Polyalkylene polyamino polykis methylene phosphonic acids and salts thereof and methods for producing same

ABSTRACT

THIS INVENTION RELATES O POLYALKYLENE POLYAMINO POLYKIS METHYLENE POSPHONIC ACIDS AND THEIR SALTS AND TO METHODS OF PREPARING THE SAME SUBSTANTIALLY FREE OF ANALOGUES THEREOF, IN WHICH AMINE RADICALS CONTAIN UNSUB-   STITUTED PRIMARY OR SECONDARY AMINE HYDROGEN, AND TO THE PROCESS FOR USING THE SAME.   D R A W I N G

June 1973 3. J. KAUTSKY 3,738,937

POLYflLKYL/ENE POLYAMINO POLYKIS METHYLENF PHOSPHONIC ACIDS AND SALTS THEREOF AND METHODS FOR PRODUCING SAME Filed May 8, 1970 f/C/ c In (WM/v7 .-5 WA 766 5 i 4 g INVENTOR. 660666 J MK/ZSKV a /ze/vpe/c/amd 505K010 A 7 TOE/V5 3 5 US. Cl. 252-480 United States Patent ABSTRACT OF THE DISCLOSURE This invention relates to polyalkylene polyamino polykis methylene phosphonic acids and their salts and to methods of preparing the same substantially free of analogues thereof, in which amine radicals contain unsubstituted primary or secondary amine hydrogen, and to the process for using the same.

The fields to which the invention relates include compounds which have the property of inhibiting the precipitation of salts from waters containing the same and processes for prevention of formation of scale such as calcium carbonate, calcium sulfate and barium sulfate,

in systems where such scale is encountered.

This invention also relates to a process for inhibition of corrosion of ferrous bodies.

This invention also relates to a process for sequestration of cations such as iron, copper and aluminum.

This invention also relates to the treatment of oil, water and gas wells to inhibit scale depositions in formations on well surfaces.

The severity of scaling increases with the concentration of the precipitating ions (Ca++ and SO or CO or Ba++ and 80 and with the temperature of water. Calcium sulfate and carbonate, as well as barium sulfate, exhibit inverse solubility with respect to temperature.

Scale is known to obstruct passage of Water and oil in producing wells and in the oil-bearing formations. It leads to thick deposits in heat exchangers and boilers, causing a poor heat transfer. It plugs filters. It plugs pores in sand and rock formations and thus causes an increase in line pressures and increase of resistance in Water disposal and in secondary oil recovery systems, requiring a general increase in pressure. Scale contributes to corrosion in pipe lines and Water lines.

Corrosion in turn accelerates the build-up of scale deposits; corroded, rough surfaces offer sites for scale crystals to adhere. The combination of corrosion and scale crystal growth leads to costly failures in industrial equipment.

As will be shown below, the compounds of my invention are corrosion as well as scale inhibitors, and thus they have the dual function of inhibiting the deposition of scale and protecting against corrosion, which cooperates in the prevention of scale and the prevention of plugging permeable systems, such as oil and water natural reservoirs.

This invention relates to compounds of the general formula:

where Patented June 12, 1973 radical in an uninterrupted chain of from at least two carbons up to and including 12 carbons, and n is from 1 to 5 moieties, in which at least one of the moieties contains an R of at least six carbon atoms, and Y is a methylene phosphonic acid radical:

Where M and M are hydrogen, alkali metal or an equivalent of a polyvalent metal ion such as zinc, calcium or ammonium, an alicyclic polyamine, or a heterocyclic amine radical; and this invention relates to the process for the production of such compounds.

The compounds of my invention, in their acid form, may be considered inner salts. Thus, for example, and without limitation of my invention, the following illustrates the nature of the inner salts:

There are thus available seven equivalents of acidic hydrogen. In like manner, salts of the compounds of my invention will also be analogous inner salts in which the salt-forming cations will neutralize acid hydrogens not so internally neutralized, as will be understood by those skilled in this art.

The acid forms of surface-active polyalkylene polyamino polykis methylene phosphonic acids have an average molecular weight in the range of about 600 to about 2,000, as determined by Thermonam analysis (ASTM Part 17 Method D2502). The preferred molecular Weight of the acid form is in the range of about 600 to 800.

As will be shown below, the compounds of my invention are chelating agents.

Characteristic of the compounds which are suitable as aforesaid are the polyalkylene polyamino polykis methylene phosphonic acids and their salts, in which the methylene phosphonic acid radicals are at least equal in number to the amino hydrogens of the alkylene amine radicals of the compounds of my invention. That is, all of the amine radicals of the polyalkylene polyamine radicals have been substituted by methylene phosphonic acid radicals and are thus substantially free of secondary and primary amine hydrogens.

The following are some examples conformable with the compounds of my invention, and which are useful in the process of my invention described herein:

and the alkali metal, alkaline earth and other polyvalent cation salts, the amino and substituted amino, primary and secondary amine salts of the foregoing.

Compounds as described above, which contain one or more equivalents of labile hydrogen per average molecular weight of the compound, are in their acid form ineffective as scale inhibitors, even through they may otherwise have the molecular Weight, nitrogen content and phosphonic acid, content to conform to the aforementioned formulas.

I have found that the presence of substantial amounts of the compound containing unsubstituted nitrogens, so as to leave a labile hydrogen associated with any of the nitrogens of the amine radical, produces compounds which, in dilute solutions, such as are used in commercial treatment of water for scale inhibition, cause precipitation of a portion of the compounds. Such compounds, at concentrations of about 5% by weight of the compound in water, a concentration frequently used in oil well operations, are unsuitable for oil field use.

I therefore desire that the polyalkylene polyamino polykis methylene phosphonic acids or the salts thereof, for use as scale preventers or corrosion inhibitors, be substantially free of such phosphonic acids or salts there of containing trivalent amino nitrogens in which all of the valences are not satisfied by methylene phosphonic acid radicals, herein referred to as the incompletely substituted analogue of the aforesaid completely substituted analogue. Thus, for example, it is desirable to exclude substantial quantities of the aforesaid analogous compounds wherein not all of the secondary and primary amine valences are satisfied by a Y radical.

A satisfactory test for determining the presence of an excessive proportion of the unsubstitued compounds, which are desired to be excluded from the subject matter of this invention, is to dissolve about 5% by Weight of the compound in water. Any turbidity of the water sufiicient to precipitate about 0.2% of the compound, i.e., more than about .4% by weight of the added compound, indicates an excessive amount of the unsubstituted product. Compounds which at such concentrations do not show the aforesaid turbidity are herein referred to as soluble in water.

For use in treatment of oil wells, water wells and gas wells, I prefer compounds which do not contain the unsubstituted amine hydrogens as aforesaid, as well as compounds which are soluble as aforesaid.

In order to prevent the formation of the incompletely substituted polyalkylene polyamino polykis methylene phosphonic acid, I have found it preferable that there be at least one phosphonic acid molecule present for each labile hydrogen in the primary and secondary amine radicals in the polyamine reactant, in the reaction mixture used to produce the resultant compound, when the re actants are condensed through the formaldehyde reaction described below.

The figure of the drawing illustrates in schematic form the apparatus referred to in the following description.

The preferred process for the formation of compounds of my invention is carried out by feeding phosphorus trichloride through 3 and sparger 31; directly into a body of water in a vessel 1, While stirring vigorously with motorized stirrer 8. The vessel is equipped with a heating jacket 2, a cooling coil 2a, and a reflux condenser 4, which is connected to a trap 5, provided with a liquid return line 6, and to a hydrochloric acid scrubbing system 8 through line 7.

The vessel is filled with the required amount of water, and phosphorus trichloride is introduced directly into the body of water to form hydrochloric acid and phosphonic acid.

I have found it preferable to introduce the PCI;.; directly into the body of water and to stir vigorously during the reaction. I also prefer to control the addition rate of the phosphorus trichloride slowly into the body of water by feeding the phosphorus trichloride underneath the body of water through the feeder pipe 3. The rate of addition must be controlled to prevent the generation of orange phosphorus and phosphine gas.

It has been found desirable that the rate of addition, when about three-quarters of the required amount of phosphorus trichloride has been added, shall be carefully monitored and introduced slowly, in order to avoid such undesirable side reactions.

A further undesirable consequence of an improper addition of the phosphorus trichloride is the distillation of hydrochloric acid which passes through the condenser and into the hydrochloric acid tower and carries phosphorous acid with it.

When all of the phosphorus trichloride has been added, and this occurs at ambient temperature, the temperature of the batch rises due to reaction exotherm, cooling is applied to hold the temperature to about 200 to 220 F, and time is allowed to complete the reaction of the PCl with water to produce the phosphorous acid. It is important that constant rapid agitation be maintained during the period of addition and the subsequent high temperature reaction stage.

By following this precaution, I find that I avoid the production of incompletely substituted compounds.

When the phosphorus trichloride has reacted, the requisite amount of polyamine is introduced into the body of the reaction mixture in the vessel 1 through 3a. The amount of amine which is added should be at least equal to a molar ratio of '1 mole of PCl or the equivalent phosphorous acid HPO(OH) for each equivalent of labile amino hydrogen in the polyalkylene polyamine employed in the reaction. When dihexylene triamine is employed, it is desirable to have at least one mole of amine to 5 moles of PCl and preferably to avoid any excess of the amine. It is desirable to have a molar excess of P01 for example, of 5% to 15%.

The temperature of addition of the amine is about to about F., and therefore the reaction mixture of the phosphonic acid should be cooled from the temperature of 200 to 230 F. down to about 100 to 120 F.

After all the amine has been added, the temperature is raised to about 200 to 220 F., and an aqeous solution of formaldehyde is added through the sparger 3b. The formaldehyde rate of addition must be controlled so that the temperature does not rise excessively, since the reaction is exothermic. The rate is controlled by the cooling coil so as to produce a steady reflux.

The molar amounts of formaldehyde which are added shall be at least equal to the molar quantities of PCI; which are used, and preferably somewhat in excesss, for example, 10% to 20% molar excess.

When all of the formaldehyde is added, the vessel, which is at a temperature of about 200 to 220 F., is held for several hours to complete the reaction and is then cooled to about F. Assuming the reaction with the dihexylene triamine, the reaction scheme is about as follows:

By employing the mixing technique described above, I may avoid the formation of substantial quantities of compounds other than the polyalkylene polyamino polykis methylene phosphonic compounds of my invention in which all of the primary amino hydrogens of the polyamine precursor have been substituted by methylene phosphonic acid radicals.

In the case of Example 1, I have found, for example, where inadequate mixing occurs, resulting in part from the introduction of the PC1 through the top of the reactor, a substantial quantity of incompletely substituted compounds is produced. For example:

YHN(CH2)0-NH(CH2)a-NHY HYN (CH2)BNH( OHzhNYa YZN(OH2)0NH(OH2)5NY2 HYN (OHi)aNY(OHz)eNHY Y=CHP (OH)2 Compounds produced by the above variant of the preferred process did not possess the solubility to the extent stated above, i.e., are not classified as soluble compounds.

The above compounds, when isolated and tested by the tests described infra, were not active as scale inhibitors.

Employing the polyalkylene polyamines as reactants to produce the aforesaid phosphonic acids of my invention, the compounds produced are soluble.

Thus, for example, the compounds of my invention set forth in the herein tables and the salts thereof will have solubilities to the degree set forth herein.

The following is an example of a preferred preparation using dihexylene amine, which will produce a dihexylene triamino penta-kis methylene phosphonic acid, which is a preferred compound for use in the process of my invention.

EXAMPLE 1 Vessel 1 is filled with 8,700 pounds of soft water. The stirrer is started. Refrigerated Water is passed through the cooling coil. Addition of P01 is started through 3 and the sparger, slowly at a steady rate of about 100 gallons per hour. The rate of addition is moderated, and cooling is applied in order to prevent the carryover of liquid through the reflux condenser.

When about 5,000 pounds of P01 have been added, the rate of addition of the PO1 is reduced to about 20 gallons per hour, until a total of 6,060 pounds has been added.

When all of the PCl has been added (and this will take about 5 hours), any condensate in trap '5 is returned to the vessel 1. The temperature of the vessel is then raised to about 220 F. and is held for about 6 hours to complete the reaction of PCI;, and to produce the phosphorous acid.

1y, since the reaction is exothermic. The rate is controlled so as to preduce a steady reflux.

When all of the formaldehyde is added (this usually takes about 5 hours), the vessel is heated to 200*2l0 F., and the mixture is held for about 6 hours to complete the reaction and then cooled to 150 F. and discharged.

For simplicity, the pure amine is included in the above reaction scheme. It will be understood, however, that the other polyamine fractions will react according to the above scheme, adjusting the molar ratios to provide for an excess of PCl and consequent excess of phosphorous acid above the stoichiometric ratios.

The above example will produce about 16,500 pounds of triamino dihexylene pentakis phosphonic acids, containing some tetramino trihexylene hexakis methylene phosphonic acid, substantially free of any phosphonic acid derivatives containing an amine hydrogen associated with an amine nitrogen, unsubstituted by the methylene phosphonic acid radical.

It will be recognized that, because of the presence of hydrochloric acid in the mixture when the amine is added, it will enter the reaction as the hydrochloric acid salt; and the reaction therefore occurs with the salt of the amine.

Because of its availability and cost, I prefer to employ the commercial product composed of about 3 mols Y2N(C H12) NY C6H12NY2 to about 1 mol Y2N(C H )NYC H NYC H NY Where the compound is referred to herein, it will be understood that it may contain the polymeric forms derived from the polyamines of higher polymeric forms referred to above.

In Example 1, the amine was composed of the triamine and the tetramine as aforesaid.

The compounds of this invention possess surfactant properties in aqueous solutions. The data and comparisons with other amino methylene phosphonic acids are shown in terms of surface tension reduction in water in Table I.

TABLE L-SURFACE TENSION 0F POLYMERIC ALKYL PHOSPHONIO [Tensiometen Du Noiiy Tensiometer, 6 mm.

ACIDS SOLUTIONS platinum rin Y in the structures below equals to CHrPO (OHM g Scale inhibitors Concentration percent by weight in distilled water Dynes/sq. em.

The mixture of phosphorous acid, hydrochloric acid and water in the vessel 1 is cooled to about 120 F., and 2200 pounds of dihexylene triamine is added in a steady stream to the body of the vessel 1. The amine is a commercial product as described hereinafter.

When all of the dihexylene triamine is added, the temperature is raised to about 215 F., and 4000 pounds of 37% aqueous formaldehyde is added through the sparger. The formaldehyde rate of addition must be controlled so that the temperature does not rise excessive- It was found that compounds which produce the surface tension reduction are outstanding scale inhibitors under dynamic conditions encountered in the field.

Comparing compounds (1)-(3) of my invention with (4)(8) and also with distilled water (9), it will be seen that the compounds of my invention are excellent surface active agents, while compounds (4)(8) are essentially inactive. This illustrates the effect of the presence of the polymeric amine radical and the advantage of the presence of the hexylene radical in the polymeric amine radical.

The following data illustrate the effectiveness of the compounds of my invention in inhibiting the crystallization of calcium sulfate and their effect upon the degree of scale protection.

Laboratory test A dynamic test of calcium sulfate crystallization in an agitated system was developed to examine the performance of various additives. The test is carried out as follows:

Solutions (A) sodium chloride in distilled water. (B) 3% calcium chloride in solution A. (C) 3% sodium sulfate in solution A.

Procedure Introduce the tested additive in the desired concentration into ml. of solution B in a 250 ml. beaker.

Place 50 ml. of solution C into another 250 ml. beaker.

Place both beakers on a hot plate and agitate.

When temperature of the liquid in the beakers has reached 140 F., pour solution B into solution C and continue to agitate for five minutes at 140 F.

Transfer quantitatively the contents from the test beaker into a 100 ml. calibrated centrifuge tube and allow to digest for /2 hour.

Centrifuge the scale for 10 minutes at a medium speed.

Read and record the volume of scale. Run a blank employing the same conditions but without the addition of the inhibitor.

The results of this test are summarized in Table H.

Analogous compounds (5), (=6) and (7), containing unsubstituted amino nitrogens, showed no scale inhibition by the above test.

Comparing the compounds of my invention (1)-(4) with compounds (5)-(9), it will be observed that the compounds of my invention are much superior. It required 10 times as much of the cyclohexylene diamino tetrakis phosphonic acid to obtain incomplete protection, while the compounds of my invention, at the lower concentrations, gave substantially complete protection.

While the ethylene diamino tetrakis phosphonic acid required conversion to the sodium salt form to be at all soluble and could not be dissolved in the acid form, it was substantially inactive. It required more than 100 times the concentration to get incomplete protection. The incompletely substituted analogues were inactive.

The result of this inhibition is the retention of the salts in solution. This is illustrated by the following data.

By inhibiting crystallization, the additives raise the concentration of CaSO and CaCO in solution. Results in a static test employing various concentrations of the sealing compounds in excess of their solubility limits, at various temperatures, are shown in Table III.

To the solutions of salts at the concentrations indicated in the table, the compounds were added in the indicated concentrations. The mixtures were allowed to stand at the indicated temperatures for the stated periods. The titration of calcium ions was performed by the Schwarzenbach method, utilizing the ethylene diamino tet- Iacetic acid as a titrant.

TABLE II.SCALE INHIBITION OF "ARIOUS POLYMERIC PHOSPONATES (Conditions: Temperature: 140 F.; concentration: Ca++ 5,000 %p.m.; S04 10 to C zPO(OH) Compound j000 p.p.m.; NIB-015%. Y in the structures below equals Concentration, Scale 1 p.p.m. of protection, compound percent (3) Morpholine salt of Yg-(CHZ)n-N(Y)(CH2)t-NYa 1 The percent scale protection is determined by dividing the difference between the volume of the scale deposited using the inhibitor and the volume of the scale produced in the blank, as the numerator, by the volume of the scale produced in the blank as the denominator multiplied by 100.

1 In the orm of the sodium salt. The acid form not neutralized by sodium was insoluble in distilled water. Only 20 parts per million could be introduced into solution.

TABLE III.CONCENTRATION OF PRECIPITATING SALTS-432.80 AND CaCOs-IN SOLU- TIONS CONTAINING SCALE INHIBITORS Hard- P.p.m. Hard- P.p.m: Cone, ness, CaSO4 ness, CaCOs p.p.m. p.p.m. 'Iemp., after p.p.m. after Additive inhibitor CaSOq F. 24 hrs. CaCOa 2 thrs.

B1901 Nfnze 15, 000 75 3, 600 225 1 Y:N(OHa)aN(Y)(CH2)aNYa. 1 300 112 (2) YaNKCHmN (Y)]2 (CH2)aNYn..-:;:::::;.{ g 112 2.4 flN(CH2)2N(Y)(CH2)2NY:..::::::::. 20:0 4.8 10.0 20.0 i; 1 Y.N oHi)flN(Y (0Hi)tNY,--=-= L; 1.'2 aN[(CH2)aN(D12(CH2)0NY2--::.;-;-:..-{ 4Z8 (3) Y2N(CHflhNH(CHa)zNH(CHz)aNYa.;;:::-{ 418 4 Y 0.0 O N 20.0 10 Blank None 7 5'1 3 0 3353 332 il 1 H NY YaN[(CH2)eN ]2(C 2):: 2 4.8 7,500 7,486 225 160 it e23- s2 2 YN CH CH NY 0 a I 4.8 7,500 7,500 225 190 4. 8 7, 500 2, 800 225 90 (3) NYa--:::: 10.0 7, 500 3,100 225 90 20. 0 7, 500 4, 600 225 100 Comparing the compounds of my invention 1) and (2) with compounds (3) and (4), it will be seen that the compounds of my invention give a substantially greater degree of scale inhibition at less than a quarter of the concentration required from compounds (3) and (4) for inferior scale inhibition.

Surface-active polymeric alkyl phosphonie acids were tested as corrosion inhibitors in sour waters containing 100,000 p.p.m. sodium chloride and 0.5 ml. of acetic acid per liter; test solutions were saturated with hydrogen sulfide and tested according to the Wheel test described by A. C. Nestle, Simulated Field Usage Testing Organic Inhibitors for Oil and Gas Wells, Materials Protection, vol. 7, p. 31, January 1968.

It will be seen that, whereas products (3) and (4) have no corrosion inhibition properties, the compounds of my invention have substantial corrosion protection properties.

The results are shown in Table IV.

TABLE IV.-CORROSION INHIBITION BY POLYMERIC ALKYL PHOSPHONIC ACIDS AND THEIR DERIVATIVES Coupon Conc., weight Percent Compound p.p.m. loss, mg. protection (1)YzN(CHz)uNY(CHi)tNY1 5;; 2) mrmumumonsmn 53 3 3 3g;

10 72.8 N11. (3) YzN(CHi)aNY(CH2)aNYa.-..:.;. 20 74.0 None. 50 76.3 D0. 10 77.1 Nil. (4) NYs::::::::::::::.-;::::- 20 76.2 None.

50 81.0 Corrosive. 71.4: Blank. 68.8 l 69.5

All tests were run for 24 hours at roomtemperature, 70 F.

Percent protection is determined as the ratio of the difference between the coupon weight loss with the blank and the coupon weight loss using the inhibitor, divided by the coupon weight loss of the blank, multiplied by Polyalkylene polyamino polykis methylene phosphonic acids of this invention show excellent compatability with cationic surface-active amines.

The resulting salts are corrosion inhibitors, as shown in Table V.

TABLE V.PERFORMANCE OF POLYMERIC ALKYL PHOS- PHONIC ACID AMINE SALTS AS CORROSION INHIBITORS Salt containing excess of acid%;quivalents of acid per 1 equivalent of am e:

NOTE.-'CO11'OSIOI1 tests were run in sour brine 24 hours at room temperature (70 F.), in the presence of constant inhibitor concentration, by the Wheel test procedure referred to previously.

Polymeric polyalkylene polyamino polykis methylene phosphonic acids of this invention exhibit chelating properties and show excellent dispersant properties for iron. Tests for dispersing power and chelation were run visually by titration of an inhibitor solution (500 p.p.m.) at constant pH with a 4% solution of ferric chloride to an end point of permanent turbidity after 10 hours standing. Results are shown in Table VI.

TABLE VI.-CHELATION AND DISPERSION OF IRON BY POLYMERIC ALKYLENE POLYAMINO POLYKIS METH- YLENE PHOSPHONATES The chelating and dispersing properties of polymeric alkyl phosphonic acids are very important in the boiler treatment, in pipe lines, and in the oil field. Additives with chelating properties remove existing deposits and contribute to cleanliness of the system.

In using the compounds of my invention as scale inhibitors, advantage is taken of the solubility product of the calcium salt of the polyalkylene polyamino polykis methylene phosphonic acid employed, at the pH of the involved water.

Thus, for example, employing the compounds formed according to Example 1, the amount of the polyalkylene polyamine polykis methylene phosphonic acid required to prevent deposition of calcium sulfate or the calcium salt of the above polyalkylene polyamine polykis methylene phosphonic acid at various pHs is as follows in Table VII.

The following table gives the concentrations of the above pentakis methylene phosphonic acid which will hold the calcium sulfate and the calcium salt of the above acid in solution at the indicated pH. The test was conducted at ambient temperature in water containing 5000 parts per million of Ca ions and 10,000 parts per million sulfate ions at 140 F.

If the concentration at the various pH values is exceeded, the calcium salt of the polykis acid precipitates. If the concentration is less than the lower limit, calcium sulfate is precipitated.

In carrying out the process of scale inhibition in systems such as water lines and pumps, boilers and hot water heaters, depending on the pH of the water and temperature encountered, I add a concentrated solution of the polyalkylene polyamino polykis methylene phosphonic acid to introduce into the water an amount of the acid which will, according to the static test described in connection with Table III, produce substantially no precipitation, as indicated by the substantial equality of the Ca ion content of the sample before and after treatment in said test.

For example, for waters of pH 6 to 8, a useful concentration of the compound to be established in the water shall be from about 10 to about 200 parts by weight per million of the polyalkylene polyamino polykis methylene phosphonic acid.

The introduction may be made into the circulating water by conventional methods.

In carrying out corrosion protection of ferrous structures in contact with waters, I may make a preliminary test, as described in connection with Table IV, to determine the concentration of the compound to give the 12 desimd protection. However, suitable protection will be found to be attained in normal water media when employing the compounds at the concentrations set forth above, i.e., 10 to 200 parts by weight per million.

By measuring the pH of the water treated, the addition rate of the polyalkylene polyamino polykis phosphonic acid employed can be adjusted to inhibit scale formation in water lines, boilers and other systems in which scale is desired to be inhibited.

In addition to the inhibition of scale, the compounds will also act as corrosion inhibitors, as described above.

An additional advantage is obtained by employing salts of the acids of my invention, particularly'the salts shown in Table V.

Particularly useful compounds are salts formed from a mixture of the following substituted morpholine compounds in the approximate mixture as follows:

(A) bis-2-(4- morpholinyl) ethyl ether, about 60%:

(B) 4 (Z-aminoethoxy) ethyl morpholine, about 25%:

/ O /NCHzCHz O-CHzCHzNHa (C) 2 (4-morpholinyl ethoxy) ethanol, about 15%:

/ O NCHzCHzO-CHz CH2 OH Such salts are particularly useful in ranges of temperature of 200 C., for Water treatment.

Other useful salts include salts of the alkyl amido polyalkylene amines, RCONHR NHR NH wherein R is alkyl chain of C to C carbon atoms and R and R are alkylene radicals of 2 to 6 carbon atoms. For example, salts of:

The compounds of my invention are also useful in the treatment of waters used in water drives and other secondary recovery methods, to inhibit scale formation in the formations, the well, lines and equipment used in connection therewith. rParticularly useful and preferred for that purpose are the substituted morpholine salts referred to above. For example, I may employ about 0.5 to 2 pounds of the compounds ofmy invention per barrels of water treated.

In many cases it is desirable to inhibit corrosion in lines of producing oil wells where also the water cut of the oil is sufficiently high so that scale deposition is a factor. In such cases, I proceed by the squeeze method to introduce either an oil-soluble form or a Water-soluble form of the compounds of my invention, in their calcium salt form, into the formation. Usually about 100 to about 1,000 pounds of the scale inhibitor of my invention are introduced into the formation.

Suitable compounds of the oil-soluble form are the amine salts, the amine cation of which is an amine such as, for example, the salt of the amine, item (D) supra, and the acid of Example 1.

For example, I may employ 200 pounds of salt from (D), which is mixed with 200 parts of ethyl alcohol and the mixture diluted 3 to 1 with an aromatic solvent such as toluene. To this mixture is added a nonionic surfactant, such as an alcohol polyethoxylate or a polyethoxylated fatty acid, or other conventional nonionic surfactant. Alternative to the ethyl alcohol I may use isopropyl alcohol, and instead of toluene I may use benzene or Xylene or mixtures thereof. The purpose is to produce a common solvent for the compound and the oil.

For example, I may introduce into the well flow tube, which has been drawn down, gallons of the above solution of the salt of Compound D, and then follow sure is applied to the oil to force the solution into the formation.

These figures are merely illustrative, and the amounts will depend on the permeability of the formation and the volume of the liner in the well, as will be understood by those skilled in this art.

This procedure may usefully be repeated periodically at intervals of about 3 to 12 months. The level of the concentration of the compound in the production stream is monitored by determining the concentration of inhibitor by oxidizing the polyphosphonic compound to orthophosphate with sulfuric acid and potassium permanganate or other suitable oxidizing agents such as perchlorate or hypochlorous acid. The phosphate is determined, for example, colorimetrically, as the phosphomolybdate complex, compared with a standard phosphate solution. The equivalent amount of the salt of D present in the sample can be determined by a simple stoichiometric calculation.

The concentration of the salt of Compound D of 10 parts per million or higher is deemed a safe level. When the content drops to as low as 5 parts per million, it is desirable to repeat the above treatment.

A particularly useful reservoir treatment to prevent scale deposition is to employ the water-soluble partial calcium salt of the phosphonic acids of my invention, for example, the alkaline earth inner salt of the polyalkylene amino pentakis phosphonic acid, as stated above, in which each of the amine nitrogens is associated with one of the protons of the acid hydroxyl groups of the phosphonic acids. Preferably a substantial portion of the remaining acid groups is neutralized with calcium, for example:

tin practice, the treatment is performed with chemically neutral (pH 6 to 7.5) solutions of the partial calcium salt containing typically from about 1.5 to about 2.5 mols of calcium per mol of the polyalkylene polyamino polykis methylene phosphonic acid.

Where the polykis phosphonic acids are made from mixtures of the polyalkylene amines, as in the case of Example 1, the calcium neutralized acid will be a mixture of the calcium salts of the various acids, as will be understood by those skilled in this art.

Further, like salts of the other polyalkylene polyamino polykis phosphonic acids described above may be used.

This treatment will inhibit the deposition of scale in the formation at the locus of the well surface. Due to the pressure and temperature gradient through which the formation fluids pass, in cases where the oil is mixed with water, scale deposition at the well locus is encountered. The scale deposits increase the flow resistance and reduce the rate of flow, i.e., the well production rate.

It is the purpose of the well treatment of my invention to deposit in the formation adjacent to the well, in the flow patterns of the well, a reservoir of the scale inhibitors of my invention. As the oil and water flow through the areas of the reservoir, they will dissolve some of the deposited inhibitor in quantities sufficient to inhibit and ideally to prevent scale deposition.

As will be seen by reference to the above, the solubility of the calcium salt depends on the pH of the solution, being highest at low pH and least at high pH.

1' take advantage of this property to deposit the calcium salt in the formation by establishing a high pH, to cause the deposition of the alkaline earth salts in the formation. Because of the limited quantity of the deposited salts, no plugging or substantially increased resistance to fluid flow is encountered. When the formation waters, which are of relatively low pH, in the neighborhood of 6.5 to 7, pass over the calcium salt which is deposited at the higher pH, the salt dissolves and is carried by the formation fluid and acts to inhibit scale formation and corrosion of the lines, pumps and tankage.

I inject into the formation a quantity of the water solution of the calcium salt at a pH of about 6 to about 7.5. The quantity injected will depend on the distance to which the injection is desired and the volume of the oil formation in which the salt is to be deposited, giving due regard to the other parameters of the oil formation.

I follow this injection with an alkaline water solution, for example, a KOH, NaOH or calcium hydroxide solution, in order to raise the pH of the environment of the injected calcium salt to precipitate the salt on the grains of the formation. As the formation fluid is produced, the water content which is at a lower pH will dissolve some of the salt; and, because of the inhibitor action of the salt, will prevent the formation of scale on the well face and the well locus and flow lines. I

The following is one example of this application of my method to a producing oil well.

A well which, due to scaling, had its production rate reduced to barrels per day, cutting 80% water. The well was shut down, and 110 gallons of the calcium salt of compounds produced according to Example 1 in 50% by weight solution at a pH of 7 were introduced into the well, which had been suitably drawn down.

The compound in the well was pressured with barrels of production water, to force the calcium salt solution into the formation.

A solution of Ca(OH) of 100 pounds dissolved in 4 barrels was pressured into the formation. This was followed with 300 barrels of produced water, to push the injected reagents into the formation to the depth required. The flow return showed that the formation fluid picked up the inhibitor and that the system was protected.

The following data give the concentration of the compound in the formation fluid, expressed as parts per million of) phosphate ion, determined in the manner described aove.

P.p.m. P0 ion Immediately after treatment 75 Two weeks later 75 Five weeks later 40 Four months later 20 is an alkylene amino methylene phosphonic acid radical containing n moieties, where R is hexylene radical, n is from 15 moieties and Y is a methylene phosphonic acid radical:

where where M and M are hydrogen, or alkali metal or an equivalent of a polyvalent metal ion or ammonium or amine radical, or salts thereof; said composition being substantially free of unsubstituted analogue of the aforesaid polyalkylene polyamino polykis phosphonic acids or salts thereof.

2. The composition of claim 1, in which the said salt is the partial calcium salt of said polyalkylene polyamino polykis methylene phosphonic acid.

3. The composition of claim 1, in which said salt is an alicyclic polyamine salt.

4. The composition of claim 1, in which the said salt is the salt of a substituted morpholine.

5. The composition of claim 1, in which R is C H and n is 1, 2, or 3.

6. The composition of claim 1, in which the polyalkylene polyamino polykis methylene phosphonic acid or salts thereof are a mixture of dihexylene triamino pentakis methylene phosphonic acid or salts thereof and trihexylene tetramino hexakis methylene phosphonic acid or salts thereof.

7. The composition of claim 6, in which the said salt is the partial calcium salt of said polyalkylene polyamino polykis methylene phosphonic acid.

8. The composition of claim 6, in which said salt is an alicyclic polyamine salt.

9. The composition of claim 6, in which said salt is a salt of is an alkylene amino methylene phosphonic acid radical where containing 12 moieties, where R is a hexylene radical, n is from 1-5 moieties and Y is a methylene phosphonic acid radical:

where M; and M are alkali metal or a polyvalent metal ion or ammonium or amine radical; said composition being substantially free of unsubstituted analogue of the aforesaid polyalkylene polyamino polykis phosphonic acids or salts thereof.

13. The composition of claim 12 in which the said salt is the partial calcium salt of said polyalkylene polyamino polykis methylene phosphonic acid.

14. The composition of claim 12, in which said salt is an alicyclic polyamine salt.

15. The composition of claim 12, in which the said salt is the salt of a substituted morpholine.

16. The composition of claim 12, in which R is C H and n is l, 2, or 3.

17. The composition of claim 12, in which the said salts are the partial calcium salts of said mixture of the polyalkylene polyamino polykis methylene phosphonic acid.

18. The composition of claim 12, in which said salts are alicyclic polyamine salts.

19. The composition of claim 12, in which said salts are salts of 20. The composition of claim 12, in which the said salts are the salts of a substituted morpholine.

21. The composition of claim 20, in which the substituted morpholine is a mixture of bis-2-(4 morpholinyl) ethyl ether, 4 (2-aminoethoxy) ethyl morpholine, and 2 (4-morpholinyl ethoxy) ethanol.

22. A composition of matter consisting essentially of a mixture of dihexylene triamino pentakis methylene phosphonic acid and trihexylene tetramino hexakis methylene phosphonic acid or salts of said acids, said composition being substantially free of unsubstituted analogue of the aforesaid polyalkylene polyamino polykis phosphonic acids or salts thereof.

23. A composition of matter consisting essentially of a Water soluble mixture of the inner salts of dihexylene triamino pentakis methylene phosphonic acid and trihexylene tetramino hexakis methylene phosphonic acid substantially free of polykis methylene phosphonic acids in which not all of the amino hydrogens have been substituted by methylene phosphonic acid groups.

References Cited UNITED STATES PATENTS 3,505,238 4/1970 Liddell 252l 3,536,752 10/1970 Crutchfield 260502.5 3,434,969 3/1969 Ralston 21058 3,619,427 11/1971 Kautsky 21058 FOREIGN PATENTS 1,069,860 5/1967 Great Britain 23l65 DANIEL J. FRITSCH, Primary Examiner US. Cl. X.R. 

